CN117920319A - Molecular sieve catalyst, preparation method and application thereof, and method for treating chloropetrochemical organic waste gas - Google Patents
Molecular sieve catalyst, preparation method and application thereof, and method for treating chloropetrochemical organic waste gas Download PDFInfo
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- CN117920319A CN117920319A CN202211302768.5A CN202211302768A CN117920319A CN 117920319 A CN117920319 A CN 117920319A CN 202211302768 A CN202211302768 A CN 202211302768A CN 117920319 A CN117920319 A CN 117920319A
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- waste gas
- molecular sieve
- organic waste
- indium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 239000007789 gas Substances 0.000 title claims abstract description 69
- 239000010815 organic waste Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 27
- AMBYFCFKKPUPTB-UHFFFAOYSA-N cobalt indium Chemical compound [Co].[In] AMBYFCFKKPUPTB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000012855 volatile organic compound Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000002471 indium Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
- F23G2209/142—Halogen gases, e.g. silane
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a molecular sieve catalyst for catalytic combustion treatment of chlorine-containing organic waste gas, a preparation method and application thereof. The preparation method comprises the following steps: mixing cobalt-indium-containing salt solution, a precipitator and an ultrastable Y molecular sieve for contact, and then separating, drying and roasting. The invention provides a method for treating chloropetrochemical organic waste gas by a catalytic combustion method. The catalyst has higher activity and can be widely applied to catalytic oxidation combustion reaction of industrial organic waste gas such as chloropetrifaction organic waste gas.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a molecular sieve catalyst for treating chlorine-containing organic waste gas by a catalytic combustion method, a preparation method and application thereof, and a method for treating chlorine-containing petrochemical organic waste gas by the catalytic combustion method.
Background
Waste gas containing Volatile Organic Compounds (VOCs) is often generated in the petrochemical production process, such as the use of chemical products such as paint, lubricating oil, organic solvents and the like, the incineration of industrial waste residues, the discharge of various tail gases, petrochemical industry and petroleum refining, the production of rubber, the frequent use of pesticides and the like all lead to the discharge of a large amount of VOCs. These exhaust gases, if discharged directly into the atmosphere, can cause significant harm to the atmosphere. Most volatile organic compounds have peculiar smell, and generate lesions and even cancerogenesis to human bodies; in particular, the volatile organic waste gas containing halogen has high toxicity, and can generate photochemical reaction with ozone to generate photochemical smog, thereby greatly damaging the global environment. Therefore, effective treatment of organic waste gas generated in the petrochemical industry process is an important topic in environmental science.
The most fundamental and effective method for treating the pollution of Volatile Organic Compounds (VOCS) is to replace the current technology by adopting a green pollution-free technology, and the emission of waste gas is controlled without or with less harmful raw materials. However, due to the limitation of the scientific and technical level, many industries related to civilian life cannot find environment-friendly technology to replace the technology, and various organic waste gases are inevitably discharged to the environment in the production and use processes. In order to alleviate the harm of these VOCS to the environment and human beings, recycling (physical method) or degradation (chemical method) technology is generally adopted at present to control the emission of VOCS. The physical method comprises an adsorption method, a condensation method, a membrane separation method and the like, is a non-destructive method, and has the advantages that volatile organic compounds can be recycled, but the treatment is not thorough, and secondary pollution is easy to cause; the chemical method mainly comprises a direct thermal combustion method, a catalytic combustion method and the like. The chemical method is characterized by thorough treatment. The thermal combustion method is to crack harmful substances in the tail gas through high temperature, the temperature of thermal cracking is up to 800-900 ℃, a large amount of fuel oil is required to be consumed, the operation cost is high, the energy consumption is high, the removal rate of halogen-containing organic matters is low, the direct combustion treatment of chlorine-containing VOCS requires higher combustion temperature, and the incomplete combustion can produce harmful substances such as CO, formaldehyde, phosgene, chloroformic acid and the like to cause secondary pollution. The catalytic combustion method reduces the operation temperature to 280-450 ℃ by means of the action of the catalyst, greatly reduces the energy consumption, is safe and stable to operate, reduces the operation cost, does not produce nitrogen oxides, and therefore does not produce secondary pollution. Therefore, catalytic combustion is an ideal method for treating petrochemical organic waste gas.
The catalyst for catalytic combustion mainly comprises: noble metal catalysts, such as Pt, pd, rh and the like, have high activity, but have poor halogen resistance, are easy to poison, and have rare resources and high price; single metal oxide catalysts, such as copper, manganese, cobalt, etc., which are relatively low cost but generally active; the composite oxide catalyst is easy to obtain, has good halogen resistance, is not easy to poison, has higher catalytic activity than the corresponding single oxide, and is prepared by loading the composite oxide of cerium, lanthanum and zirconium on honeycomb ceramics or alumina to prepare a catalytic combustion catalyst, and loading noble non-noble metal oxide on a molecular sieve carrier in situ.
Disclosure of Invention
The invention aims to solve the problems of high price, poor toxicity resistance and the like of a catalyst for catalytic combustion of a noble metal in the presence of a petrochemical-containing organic waste gas in the prior art, and provides a molecular sieve catalyst for catalytic combustion treatment of the chlorine-containing organic waste gas.
In order to achieve the above object, the present invention provides in one aspect a molecular sieve catalyst for catalytic combustion treatment of chlorine-containing organic exhaust gas, the catalyst comprising a supported ultrastable Y molecular sieve, and active metal components cobalt and indium.
In a second aspect, the present invention provides a method for preparing the molecular sieve catalyst of the present invention, comprising: and mixing and contacting the cobalt-indium-containing salt solution, the precipitator and the ultrastable Y molecular sieve, and then separating, drying and roasting.
The catalyst prepared by the invention has the characteristics of high activity, high halogen resistance and high water resistance.
The third aspect of the invention provides the application of the catalyst in the catalytic combustion of the petrochemical-containing organic waste gas.
The molecular sieve catalyst prepared by the invention has higher activity and can be widely applied to catalytic oxidation combustion reaction of industrial organic waste gas such as chloropetrifaction organic waste gas.
In a fourth aspect, the present invention provides a method for treating a petrochemical-containing organic exhaust gas by catalytic combustion, the method comprising: in the presence of the catalyst, oxygen-containing gas is introduced at 200-500 ℃ to burn the petrochemical organic waste gas.
The molecular sieve catalyst can catalyze and burn the chloropetrifaction organic waste gas to generate carbon dioxide and water at a lower temperature.
Under the condition that the chlorohydrination-containing organic waste gas component contains chloropropene and epichlorohydrin, when the temperature of a catalyst bed is above 420 ℃, the conversion rate of the chloropropene and the epichlorohydrin is above 99%, and the selectivity of the final product carbon dioxide is above 99%.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a molecular sieve catalyst for catalytic combustion treatment of chlorine-containing organic waste gas, which comprises a carrier ultrastable Y molecular sieve, and active metal components of cobalt and indium.
According to a preferred embodiment of the invention, the molecular sieve catalyst has a BET specific surface area of 200 to 800m 2/g, preferably 300 to 700m 2/g. By adopting the foregoing preferred embodiment, the catalyst performance can be further improved.
In the present invention, the content of the active metal component of the molecular sieve catalyst is not particularly required as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the total mass content of cobalt and indium in terms of oxide is 0.1 to 10%, preferably 1 to 5%. By adopting the foregoing preferred embodiment, the catalyst performance can be further improved.
In the present invention, the molar ratio of cobalt to indium as the active metal component is not particularly limited as long as the object of the present invention can be attained, and according to a preferred embodiment of the present invention, the molar ratio of cobalt to indium as the active metal component is (1 to 25): 1, preferably (4 to 22): 1. By adopting the foregoing preferred embodiment, the catalyst performance can be further improved.
In the present invention, the molecular sieve catalyst having the aforementioned characteristics can achieve the object of the present invention, and there is no particular requirement for a preparation method of the molecular sieve catalyst, and according to a preferred embodiment of the present invention, the preparation method of the molecular sieve catalyst comprises: and mixing and contacting the cobalt-indium-containing salt solution, the precipitator and the ultrastable Y molecular sieve, and then separating, drying and roasting.
According to a preferred embodiment of the invention, the contacting is preferably carried out under dynamic conditions, such as stirring, the conditions of which are not particularly critical and are determined according to the operating requirements.
The catalyst prepared by the invention has the characteristics of high activity, high halogen resistance and high water resistance.
According to a particularly preferred embodiment of the present invention, the preparation method, wherein the contacting conditions include: the temperature is 40-95 ℃ and the time is 1-5 hours.
According to a particularly preferred embodiment of the present invention, the preparation method, wherein the contacting conditions further comprise: the method is carried out under the water bath condition, and the precipitant is added into the mixed solution of cobalt-indium-containing salt and the ultrastable Y molecular sieve in a dropwise manner.
In the present invention, the precipitant may be selected conventionally in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the precipitant is selected from at least one of ammonia and urea. By adopting the foregoing preferred embodiment, the catalyst performance can be further improved.
In the present invention, the molar ratio of the precipitant to the active component is not particularly required as long as the object of the present invention can be attained, and according to a preferred embodiment of the present invention, the molar ratio of the precipitant to the active metal component element is (10 to 30): 1. By adopting the foregoing preferred embodiment, the catalyst performance can be further improved.
In the present invention, the concentration of the cobalt indium-containing salt solution is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the concentration of the cobalt indium-containing salt solution is 0.05 to 5mol/L. By adopting the foregoing preferred embodiment, the catalyst performance can be further improved.
In the present invention, the cobalt salt and the indium salt may be conventional choices in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the cobalt salt and the indium salt are each selected from one or more of nitrate, acetate and hydrochloride, and in the present invention, in the example, cobalt nitrate hexahydrate is used as the cobalt salt to exemplify the advantages of the present invention, and indium nitrate monohydrate is used as the indium salt to exemplify the advantages of the present invention, but the present invention is not limited thereto.
In the present invention, the conditions for drying in the production method may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the conditions for drying include: the temperature is 80-120 ℃, the drying time is determined according to the requirement, and the drying time is preferably 2-5 hours for the invention. By adopting the foregoing preferred embodiment, the catalyst performance can be further improved.
In the present invention, the conditions of firing in the production method may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the conditions of firing include: the temperature is 500-650 ℃, the roasting time is determined according to the requirement, and for the invention, the roasting time is preferably 3-8 hours. By adopting the foregoing preferred embodiment, the catalyst performance can be further improved.
In another aspect, the invention provides the use of the catalyst of the invention in catalytic combustion of petrochemical-containing organic waste gas.
The invention also provides a method for treating the chloropetrochemical organic waste gas by a catalytic combustion method, which comprises the following steps: in the presence of the catalyst, oxygen-containing gas is introduced at 200-500 ℃ to burn the petrochemical organic waste gas.
In the present invention, the oxygen-containing gas is not particularly limited, and a common oxygen-containing combustion gas can be used in the present invention, and according to a preferred embodiment of the present invention, the oxygen-containing gas is a mixed gas of an inert gas and oxygen or air.
According to a preferred embodiment of the present invention, the chlorohydrination organic waste gas contains one or more of chloropropene and epichlorohydrin volatile organics.
According to a preferred embodiment of the invention, the chloropropene content of the chlorohydrination organic waste gas is 0-3000mg/m 3, preferably 1000-2000mg/m 3 and the epichlorohydrin content is 0-3000mg/m 3, preferably 1000-2000mg/m 3.
According to a preferred embodiment of the invention, the volume content of water in the petrochemical organic waste gas is in the range of 0 to 10%, preferably 2 to 6%.
Under the condition that the concentrations of chloropropene and epichlorohydrin which are components of the petrochemical organic waste gas are 3000mg/m 3, when the temperature of a catalyst bed is above 420 ℃, the conversion rate of chloropropene and epichlorohydrin is above 99%, and the selectivity of carbon dioxide which is a final product is above 99%.
The present invention will be described below by way of specific examples, but the scope of the present invention is not limited to the scope covered by the examples, wherein the molecular sieve catalyst of the present invention is evaluated by: under the gas space velocity of 20000ml g -1·h-1, the catalytic combustion reaction of the chlorpetrifaction organic waste gas is carried out under the catalysis of the catalyst. The chloropropene content in the chloropetrifaction organic waste gas is 1500mg/m 3, the epichlorohydrin content is 1500mg/m 3, and the water content is 5%.
Example 1
6.5G of cobalt nitrate hexahydrate and 0.57g of indium nitrate monohydrate were dissolved in 150g of water to obtain a solution thereof, and then 30g of ultrastable Y2 was added to the above solution. 112.6g of 15% wt aqueous ammonia was added dropwise to the above solution under stirring and 67.5℃water bath, and the mixture was maintained for 3 hours. The slurry obtained above was filtered, and the obtained solid was dried at 100℃for 4 hours, and then calcined at 550℃for 4 hours to obtain a catalyst. The mass content of the cobalt-indium-containing non-noble metal oxide of the catalyst is 3%, and the specific surface area of the catalyst is 500m 2/g. And finally, carrying out evaluation test on the catalyst by tabletting and forming.
The catalytic combustion reaction of the organowaste gas containing the organochlorine was carried out under the catalysis of the above catalyst in an air atmosphere at a gas space velocity of 20000 ml/g -1·h-1 under the temperature-programmed condition from 200℃and the reaction results are shown in Table 1. The chloropropene content in the chloropetrifaction organic waste gas is 1500mg/m 3, the epichlorohydrin content is 1500mg/m 3, and the water content is 5%.
Example 2
3.5G of cobalt nitrate hexahydrate and 0.77g of indium nitrate monohydrate were dissolved in 150g of water to obtain a solution thereof, and then 30g of ultrastable Y1 was added to the above solution. 33.6g of 15wt% ammonia water was added dropwise to the above solution under stirring and 40℃water bath conditions, and the mixture was stirred for 3 hours after the completion of the addition. The slurry was filtered, and the resulting solid was dried at 100℃for 4 hours, and then calcined at 550℃for 4 hours to obtain a catalyst. The mass content of the cobalt-indium-containing non-noble metal oxide of the catalyst is 1%, and the specific surface area of the catalyst is 300m 2/g. And finally, carrying out evaluation test on the catalyst by tabletting and forming.
The catalytic combustion reaction of the organowaste gas containing the organochlorine was carried out under the catalysis of the above catalyst in an air atmosphere at a gas space velocity of 20000 ml/g -1·h-1 under the temperature-programmed condition from 200℃and the reaction results are shown in Table 1. The chloropropene content in the chloropetrifaction organic waste gas is 1500mg/m 3, the epichlorohydrin content is 1500mg/m 3, and the water content is 5%.
Example 3
11G of cobalt nitrate hexahydrate, 0.60g of indium nitrate monohydrate and 71.4g of urea were dissolved in 150g of water to obtain a solution thereof, and then 30g of ultrastable Y3 was added to the above solution. The above solution was heated to 95℃in a water bath and stirred for 3 hours. The slurry was filtered, and the resulting solid was dried at 100℃for 4 hours, and then calcined at 550℃for 4 hours to obtain a catalyst. The mass content of the cobalt-indium-containing non-noble metal oxide of the catalyst is 5%, and the specific surface area of the catalyst is 700m 2/g. And finally, carrying out evaluation test on the catalyst by tabletting and forming.
The catalytic combustion reaction of the organowaste gas containing the organochlorine was carried out under the catalysis of the above catalyst in an air atmosphere at a gas space velocity of 20000 ml/g -1·h-1 under the temperature-programmed condition from 200℃and the reaction results are shown in Table 1. The chloropropene content in the chloropetrifaction organic waste gas is 1500mg/m 3, the epichlorohydrin content is 1500mg/m 3, and the water content is 5%.
Example 4
The procedure of example 1 was followed, except that the specific surface area for preparing ultrastable Y was varied, and the specific surface area of the final catalyst was 200m 2/g, and the results are shown in Table 1.
Example 5
The procedure of example 1 was followed except that the loading of the catalyst active component was 0.5%, and the results are shown in Table 1.
Example 6
The procedure of example 1 was followed except that the molar ratio of cobalt to indium as the active ingredient was 25:1, and the results are shown in Table 1.
Example 7
The procedure of example 1 was followed except that the precipitant was NaOH, and the results are shown in Table 1.
Example 8
The procedure of example 1 was followed except that the molar ratio of precipitant to active ingredient was 8, the results are shown in Table 1.
Example 9
The procedure of example 1 was followed except that the temperature of the water bath at the time of precipitation was 30℃and the results are shown in Table 1.
Comparative example 1
6.5G of cobalt nitrate hexahydrate and 0.57g of indium nitrate monohydrate were dissolved in 150g of water to obtain a solution thereof, and then 30g of alumina was added to the above solution. 112.6g of 15wt% ammonia water was added dropwise to the above solution under stirring and a water bath at 67.5℃and stirred for 3 hours after the completion of the addition. The slurry was filtered, and the resulting solid was dried at 100℃for 4 hours, and then calcined at 550℃for 4 hours to obtain a catalyst. The mass content of the cobalt-indium-containing non-noble metal oxide of the catalyst is 3%, the specific surface area of the catalyst is 500m 2/g, and finally the catalyst is subjected to compression molding for evaluation test.
The catalytic combustion reaction of the organowaste gas containing the organochlorine was carried out under the catalysis of the above catalyst in an air atmosphere at a gas space velocity of 20000 ml/g -1·h-1 under the temperature-programmed condition from 200℃and the reaction results are shown in Table 1. The chloropropene content in the chloropetrifaction organic waste gas is 1500mg/m 3, the epichlorohydrin content is 1500mg/m 3, and the water content is 5%.
Comparative example 2
11G of cobalt nitrate hexahydrate, 0.60g of indium nitrate monohydrate and 71.4g of urea were dissolved in 150g of water to obtain a solution thereof, and then 30g of alumina was added to the solution. The above solution was heated to 95℃in a water bath and stirred for 3 hours. The slurry was filtered, and the resulting solid was dried at 100℃for 4 hours, and then calcined at 550℃for 4 hours to obtain a catalyst. The mass content of the cobalt-indium-containing non-noble metal oxide of the catalyst is 5%, and the specific surface area of the catalyst is 500m 2/g. And finally, carrying out evaluation test on the catalyst by tabletting and forming.
The catalytic combustion reaction of the organowaste gas containing the organochlorine was carried out under the catalysis of the above catalyst in an air atmosphere at a gas space velocity of 20000 ml/g -1·h-1 under the temperature-programmed condition from 200℃and the reaction results are shown in Table 1. The chloropropene content in the chloropetrifaction organic waste gas is 1500mg/m 3, the epichlorohydrin content is 1500mg/m 3, and the water content is 5%.
Comparative example 3
The procedure of example 1 was followed except that indium nitrate was not used, cobalt nitrate hexahydrate was used in its entirety, and the amounts of active ingredients used were unchanged, and the results are shown in Table 1.
7.02G of cobalt nitrate hexahydrate was dissolved in 150g of water to obtain a solution thereof, and then 30g of ultrastable Y1 was added to the above solution. 112.6g of 15wt% ammonia water was added dropwise to the above solution under stirring and a water bath at 67.5℃and stirred for 3 hours after the completion of the addition. The slurry was filtered, and the resulting solid was dried at 100℃for 4 hours, and then calcined at 550℃for 4 hours to obtain a catalyst. The mass content of the cobalt-containing non-noble metal oxide of the catalyst is 3%, the specific surface area of the catalyst is 500m 2/g, and finally the catalyst is subjected to an evaluation test by tabletting and forming.
The catalytic combustion reaction of the organowaste gas containing the organochlorine was carried out under the catalysis of the above catalyst in an air atmosphere at a gas space velocity of 20000 ml/g -1·h-1 under the temperature-programmed condition from 200℃and the reaction results are shown in Table 1. The chloropropene content in the chloropetrifaction organic waste gas is 1500mg/m 3, the epichlorohydrin content is 1500mg/m 3, and the water content is 5%.
Table 1: catalyst composition and performance tables for examples and comparative examples
In Table 1, T1 represents the lowest inlet temperature at which the conversion of chloropropene is 99% or more, and T2 represents the lowest inlet temperature at which the conversion of epichlorohydrin is 99% or more.
The above table data may be based on the embodiment data if the writing errors are inconsistent with the embodiment.
In the present invention, the reaction is evaluated by using a programmed temperature, the lowest inlet temperature means that the conversion rate reaches 99% of the lowest temperature, and the selectivity of carbon dioxide=the amount of substrate converted into carbon dioxide is 100/(the amount of substrate converted into carbon dioxide+the amount of substrate converted into other substances).
As can be seen from the results of Table 1, the molecular sieve catalyst of the present invention has significant performance advantages over conventional alumina-supported catalysts.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A molecular sieve catalyst for catalytic combustion treatment of chlorine-containing organic waste gas, characterized in that the catalyst comprises a carrier ultrastable Y molecular sieve, and active metal components cobalt and indium.
2. The molecular sieve catalyst of claim 1, wherein the molecular sieve catalyst has a BET specific surface area of from 200 to 800m 2/g, preferably from 300 to 700m 2/g.
3. The molecular sieve catalyst according to claim 1 or 2, wherein the total mass content of cobalt and indium, calculated as oxides, in the molecular sieve catalyst is 0.1-10%, preferably 1-5%; and/or
The molar ratio of cobalt to indium is (1 to 25): 1, preferably (4 to 22): 1.
4. A process for preparing the molecular sieve catalyst of any of claims 1-3, comprising: and mixing and contacting the cobalt-indium-containing salt solution, the precipitator and the ultrastable Y molecular sieve, and then separating, drying and roasting.
5. The production method according to claim 4, wherein the conditions of the contact include: the temperature is 40-95 ℃ and the time is 1-5 hours.
6. The process according to claim 4 or 5, wherein,
The precipitant is ammonia water and/or urea; and/or
The mol ratio of the precipitant to the active metal component element is (10-30): 1; and/or
The concentration of the cobalt-indium-containing salt solution is 0.05 mol/L-5 mol/L; and/or
The cobalt salt and the indium salt are each selected from one or more of nitrate, acetate and hydrochloride.
7. The process according to any one of claim 4 to 6, wherein,
The drying conditions included: the temperature is 80-120 ℃ and the time is 2-5 hours; and/or
The roasting conditions include: the temperature is 500-650 ℃ and the time is 3-8 hours.
8. Use of a catalyst according to any one of claims 1-3 for catalytic combustion of petrochemical organic exhaust gases.
9. A method for treating chloropetrochemical organic waste gas by a catalytic combustion method, which is characterized by comprising the following steps: an oxygen-containing gas is introduced at 200 to 500 ℃ in the presence of the catalyst according to any one of claims 1 to 3, and the petrochemical-containing organic waste gas is combusted.
10. The method of claim 9, wherein,
The oxygen-containing gas is mixed gas of inert gas and oxygen or air; and/or
The chlorohydrination-containing organic waste gas contains one or more of chloropropene and epichlorohydrin volatile organic compounds;
Preferably, the chloropropene content in the chloropetrochemical organic waste gas is 0-3000mg/m 3, preferably 1000-2000mg/m 3;
And epichlorohydrin content of 0-3000mg/m 3, preferably 1000-2000mg/m 3;
And/or
The volume content of water in the chloropetrochemical organic waste gas is 0-10%, preferably 2-6%.
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